Production of catalytically cracked gasoline



' May lfl, 1946.

' G. c. MONTGOMERY ETAL PRODUCTION OF CATALYTICALLY CRAGKED GASOLINE 2 sheets-sheet 1 Filed Jan. 8, .1945` mwmi ./.Lunomn l BEEN,

smdcl. mdosdv CEEOU Y PRODUCTION oF CATALYTICALLY bRACKED GAsoLINE May 14 194& G. c. MoNTGoMERY ETAI.

Filed Jah. 8, 1945 2 Sheets-Sheet 2 @conm wat.

stak w VEG NN nm worm t5.. 1 0 USQM lnvenfors: Gcorqz C. Morrqomerg CRACKED GASOLINE "George c.Y Montgomery and nulonw. momie, Wilmingto alii., assignors' to Shell Development Company, San Francisco, Calif., a corporation of Delaware u M `rAllliilftlon January s, i945, serial No. 571,830

r This invention relates to the production of normaliygaseous products and .normally lliquid hydrocarbon products of the ynature of gasoline' by the .catalyticcracking of hydrocarbon oils with clay-typev cracking catalysts :and relates more particularly lto anjsimprovedy method for the .separation-and recoverylof said products from the cracked' hydrocarbon productof said catalytic cracking treatment.

The object-of. the invention-is to provide an improvedmethod `for-'the separation and recovery of normally gaseous products and normally liquid hydrocarbon products :ofthe'nature oi gasoline from the cracked products obtained by the catalytic cracking oi hydrocarbon oils with clay-type cracking-catalysts.`- l

The cracking` of hydrocarbon oils such as gas oils, stove oils, heavy naphthas, reduced crudes,

V and the like is-us'ually 'carried out for the purpose of producing*'valuable hydrocarbon -gases lsuch as the C3 andvCr oleiins orior the purpose' of producing normally liquid products of thenature of gasoline or` for both of these' purposes. In any certain selected natural clays and earths, modiiied clays, and various synthetic clay-type catalysts.

The clays are sometimes used in theirl natural' state but are usually treated and/or modiiied, for

instance. by acid washing, removing iron-bearing impurities, leaching out alumina, adjusting the ratio of silica yto alumina and/or by incorporating J minor amounts of promoters in order to increase their activity, stability, etc., and to reduce their carbon forming tendency. Various synthetic clay-,type cracking catalysts are also now widely used. These catalysts consist largely of silica and/or alumina and/or magnesia, and are often modified by minor amounts of such materials as suitable conditions of pressure and'residence time at a temperature in the order of 800 F. to 1050 F.

case cracking to produceeither of these products produces yappreciable amounts'of the otherproduct. These products cannot be used together and it is therefore the universal practice to'separate and recover them as separateproducts. This is most commonlyeiected by condensing the major 'part ofthe normally liquid lhydrocarbons by indirect heat exchange and subjecting 'the remainder to one or more 'compression and cooling stages to condense further quantities of hydrocarbon products. A soy-called dry gas consisting essentially of materials having a molecular weight below propylene is'` then separated andremoved. 'I'his is usually done by means of rectified absorption. The Ca-C4 fraction is then generally sepal rated from the liquid product leaving a debutanized gasoline. The Cs-C4 fraction so obtained is` used either for the production of additional amounts of high grade gasoline components by polymerization, alkylation, or the like, or is used for the production of valuable chemicals such Aas v alcohols, ketones, aldehydes, butadiene, etc.

In recentl yearsthe older thermalv cracking methods have been largely supplanted by more modern catalytic cracking processes. These processes, while they differ widely in the means of contacting the catalyst with the oil to be cracked, aresimilar in that'all of them utilize a catalyst of the same general type yandall of them catalysts.

produce products of the same general character.

The catalysts used in these processes comprise I5 mospheres and-that at leasa mol excess ofwater vrectified absorber.

traced to the eiiect of traces. of nitrogen com- Y depending upon the particular hydrocarbon feed,

the'particular catalyst andthe particular results desired .Then vaporous product containing cracked and uncracked material is partially cooled ,to condense uncracked and insufliciently Vcracked ymaterial which yis withdrawn. The remainingl vvapor consists essentially of normallyl gaseous products and normally liquid products of the nature of gasoline. This material is then separated into adry gas fraction, a Ca-Cr fraction which is usually -used as an alkylation feed, and a debutanized gasoline vfraction by the method outlined above.

Plant experience has shown, however, that in the ,recovery of these products from catalytic cracking operations with clay-type catalysts considerable -diiiiculty is encountered with fouling andcorrosion ofthe equipment, particularly the 'Ihese troubles'have been pounds formed when using clay-type cracking I'he nitrogen compounds are present only in n unsuccessful. It is now found that due apparently to azeotropyA these materials (certain cyanides) are present largely in the vapor. phase and that they` can be1 effectively removed by treating the normally gaseous portion of the product while under pressure with copious amounts of water.

Furthermore, they It-is found that the treatment of the normally gaseous portion of the product with water should beV carried out-under a pressure ofat least 3 atwith respect to the normally gaseous portion of the product, and preferably' considerably more, should be employed. (A mol excess of water is an. vamount of water greater than 1 gm. mol per each 22.4 liters of the gas or vapor treated as measured under standard conditions.) It is furthermore found that thenormally gaseousportion of the product should be contacted very thoroughly with"v the water as by injecting the water in the form of a fog or fine spray into the compressed normally gaseous products or by passing the compressed normally gaseous products up through an efiicient scrubber such as a bubble tower or packed column. Furthermore, it is found that it is advantageous to-flrst contact the total reaction product with water to remove ammonia and then use the ammoniacal aqueous solution to treat the normally gaseous products. When the normally gaseous portion of the products of such catalytic cracking processes are treated in the described manner little or no fouling or corrosion of the equipment, axlid particularly the rectified absorber, takes p ace.

The processo! the invention will be described in more detail in connection with typical operations. To assist in this description reference is had to the attached drawings wherein there are shown by means of conventional ilgures -not drawn to scale two assemblies of conventional apparatus'arranged for operation in accordance with the processor the invention. Referring to the drawings. vFigure I, the catalytic cracking operation is considered as taking place in the .catalytic cracking unit I in the presence of a clay-type cracking catalyst. Since the'actual mechanics of the cracking operation per se do not enter into the invention the catalytic cracking Vunit is indicated simply by a labelled rectangle.' The product from the catalytic cracking operation consistsing of gas, gasoline, and uncracked products in the vapor state passes via line- 2 to a fractionating column 3 ofvconventional design. Heavy oil such as gas oil is removed via line l, side stripper t and line B. 'I'he vaporous product removed overhead via line 1 consists essentially of normally gaseous products and normally liquid products of the nature of gasoline. material is cooled by a combination of dire and indirect-heatexchange suicient to condense the bulk of the normally liquid products. Thus.. water is injected via line 8 preferably as a spray and the mixture is further contacted and cooled in cooler 9. 'The amount of water inJected at this point is substantial and is preferably suchthat water is in mol excess with respect to the liquid hydrocarbon condensate. This water serves a multi-fold purpose. I t extractsI the major amount oi' the small amount of ammonia invariably present in 'the products from catalytic cracking operations `with clay-type cracking catalysts. This not only scooling. The mixture of water and hydrocarbon products passes via line I to a separator II wherein it is separated into a gaseous phase consisting essentially of normally gaseous hydrocarbon products, a liquid hydrocarbon phase of the nature of gasoline, and a lower aqueous phase.

The lower 'aqueous phase containing small drawn via line I2 to a surge tank I3. The gas phase and liquid hydrocarbon phase are separately withdrawn via lines Il and I5. The gas phase is compressed by compressor I6 to a pressure above 3 atmospheres, for example between about 10 atmospheres and 20 atmospheres, and passed via line Il to the bottom of a scrubbing tower It., An amount of water in mol excess Awith respect to the gas is introduced into the scrubbing tower via lines Il and 20, and after passing through the scrubbing tower it is removed via line 2i. The compressed gas after passing through the scrubbing tower in intimate contact with the moi excess of wafer is top of the rectified absorber via line 25. A liquid hydrocarbon fraction consisting essentially of gasoline and containingthe C: and C4 components of the product in solution is withdrawn from the rectified absorber via'line 26. This fraction may be *subsequently separated into a Cs-Cl fraction and a debutanized gasoline in a conventional so-called debutanizer column (not shown). y

As pointed out above, the productsv of catalytic cracking with clay-type cracking catalysts invariably contain small amounts of ammonia. This ammonia is largely extracted by the water injected via line 8 andis found in the aqueous layer withdrawn from separator II to surge tank I3. This very dilute aqueous solution of ammonia (pH about 8.5-0) is superior to fresh water in the subsequent water treatment due to its mild alkalinity. Thus, according to a preferred embodiment of the invention water from surge tank I3 is used to treat the compressed vapors. This -water may be passed to the scrubber I0 via lines 21 and 2l. Excess water. if any. may be withdrawn via line 2l.

The described operation is very effective in eliminating fouling and corrosion troubles in the 'rectied absorber but has a disadvantage that verylarge amounts of water are required.

' Thus, in a typical cracking plant cracking 15,000

barrels per day of oil, the amount of water injeoted via line I may be, for example, in the order of 20,000 pounds per hour and that fed to scrubber Il may be, for example, anywhere from 20,000 pounds per houxup to, for instance, 120,000 pounds per hour. This water-is preferably treatedwater, i. e.. softened water. By utilizing the condensate from separator I I in scrubber Il, not only is the treatment made more effective but the amount of water required is greatly reduced.

A suitable treatment may also be carried out in the manner illustrated in Figure II of the drawings. Referring to Figure II, the vaporous hydrocarbon product from the catalytic 'cracking unit I passes tofractionating column 3 as described above in connection with Figure I. Water in an amount such as indicated is injected into the vapor stream via line 0 and the mixture is further cooled and passed to separator II as previously described. The lower aqueous phase is withdrawn via line I2 to surge tank I3. The upper gas phase is withdrawn via line I4 and is compressed by compresser I8 to a pressure of at amounts of ammonia (pH about 8.5 to 9) is with- 'la4 least 3 atmospheres. A quantity of water in mol excess with respect to the compressed vapor is injected into the compressed vapor via line 20. This water is preferably injected by a vplurality of nozzles such as 20a,.20b and `20c`asva fog or fine mist. vNozzles of the type which atomize the water by means of impin'ging' streams arefound to be quite suitable. Simple sprays are relatively Vinefcient and if they are used much greater quantities of water are necessary for -optimum eilciency. 4The liquid hydrocarbon phase from separator li is withdrawn via line I5 and pump 24. 'This stream may advantageously'be injected into the compressed vapor streamA containing the fog of water prior to passing the mixture to the cooler 30. The mixture then passes via line 3i to a second or high pressure separator 32 wherein it is separated into an upper gas phase, a liquid hydrocarbon phase and a lower aqueous phase.

' The aqueous phase is withdrawn via line 33. The' compressed gas is passed to the rectified absorber 23 via line 22. The liquid hydrocarbon phase is passed tothe rectied absorber by line 34 and pump .35. The rectified absorber is .operated in the conventional manner under conditions to producedry gas which is withdrawn via line 25.

c Inthis process, vas in the process illustrated inv Figure I, it is advantageous and desirable to use the dilute ammoniacal aqueous phase from separator Il to treat the compressedvapors. Thus, this material may be fed from-the s urge tank I3 to the fog nozzles via lines 21 and 20. Excess water, if any, may be withdrawn via line 23.

While in the above the process of the invention has been described with 'a single compression of the gaseous portion of the product, it will be understood that two or more compression states may be applied. In'such cases the treatment of the compressed vapors may -be eifected at any point or points where-the pressure is at least 3 atmospheres. `The treatment is preferably effected, however, atthe highest compression stage j where the pressure is usually in the order of atmospheres. We as our invention:

1. In a process for the production of normally gaseous hydrocarbon products and normally liquid hydrocarbon products of the nature of gasoline from hydrocarbon oils containing nitrogen compounds by catalytic cracking with vclay4type l cracking catalysts, the combination of process steps comprising condensing the maior portion of the normally liquid hydrocarbons of the nature of gasoline from the vaporous cracked products of said catalytic crackingtreatment in the presence of added water, compressing the uncondensed vapors to a pressure of at least 3 atmospheres, intimately contacting said vapors while in said compressed state with amol excess oi water thereby to extract cyanides, separating said water containing extracted cyanides and contacting the compressed gas with said lirst liquid hyy drocarbon condensate under rectined absorption conditions.v

.2. In a process for the production of normally gaseoushydrocarbon products and normally liquid hydrocarbon products of the lnature of gaso- 'line from hydrocarbon oils containing nitrogen bon phase and a lower aqueous phase, compressing the uncondensed'vapors to a pressure of at least-3 atmospheres, intimately contacting said vapors while iri said compressed state with ar'nol yexcess of said lower aqueous phase thereby to extract cyanides, separating said aqueous phase containing 'extracted cyanides, and contacting the compressed gas with said first liquid hydrocarbon condensate under rectified absorption conditions.

3.. In a process for the production of normally.

gaseous hydrocarbon products and normally liquid hydrocarbon products of the nature of gasoline from -hydrocarbon oils containing nitrogen compounds by catalytic cracking with clay-type cracking catalysts, the combination of process steps comprising condensing the major portion of the normally liquid hydrocarbons of the nature of' gasoline from the vaporous cracked products of said catalytic cracking treatment in the pre'sence of added Water, compressing the uncondensed vapors to a pressure of at least 3 atmospheres, injecting .a mol excess of water in the form of a ne mist or fog into said vapors while e in said compressed state to extract cyanides, separating said water containing extracted cyanides Aand contacting the compressed gas with said rst liquid hydrocarbon condensate v under rectied absorption conditions.

4. In a process for the productionrof normally gaseous hydrocarbon products and normally liquid hydrocarbon products of the natureof gasoline from hydrocarbon oils containing 4nitrogen A.

compounds by catalytic cracking with clay-type cracking catalysts, the combination of process steps comprising condensing the maior portion of the -normally liquid hydrocarbons of the nature of gasoline from the vaporous cracking products of said catalytic cracking treatment in the presence oi' added water, separating the resultant mixture into a gaseous phase, a liquid hydrocarbon phase and a lower aqueous phase, compressing the uncondensed vapors to a pressure of -at least 3 atmospheres, injecting a' mol excess of said lower aqueous phase in the form of a ne mist or fog into said vapors while in said comlpressed state to extract cyanides, separating said aqueous phase containing extracted cyanides and 'contacting thecompressed gaswith said ilrst liquid hydrocarbon condensate under rectied absorption conditions.

I c lGEORGE C. MONTGOMERY. l .,tvfnfiRUL-.ON W. McOMIE. 

